CN102507002B - Optical fiber microprobe of tip-enhanced Raman spectrometer - Google Patents
Optical fiber microprobe of tip-enhanced Raman spectrometer Download PDFInfo
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- CN102507002B CN102507002B CN201110354369.9A CN201110354369A CN102507002B CN 102507002 B CN102507002 B CN 102507002B CN 201110354369 A CN201110354369 A CN 201110354369A CN 102507002 B CN102507002 B CN 102507002B
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Abstract
The invention relates to a Raman spectrometer, and particularly discloses an optical fiber microprobe of a tip-enhanced Raman spectrometer, which includes a box body and a circuit part, wherein the circuit part is arranged in the box body; a white light imaging optical path, a laser optical path and a signal collecting optical path are arranged on the circuit part; all the white light imaging optical path, the laser optical path and the signal collecting optical path adopt optical fiber conduction; an optical fiber, a first beam splitter, a second beam splitter, a microlens, a lens, a reflector, a camera and a pull rod are arranged on the white light imaging optical path; a laser, a single mode polarization maintaining optical fiber, a optical fiber coupler, a laser-line bandpass filter plate and a 45 DEG edge filter plate are arranged on the laser optical path; and a 0 DEG edge filter plate, optical fiber coupler, a multimode fiber and a spectrometric detector are arranged on the signal collecting optical path. The invention has the advantages that the optical fiber microprobe of the tip-enhanced Raman spectrometer has simple optical path and small volume, can conveniently replace laser wave length and polarization direction, is highly stable, can be combined with any scanning probe microscope, can conveniently switch the excitation mode, and can improve the integral stability and the operation convenience of the TERS instrument.
Description
Technical field
The present invention relates to a kind of Raman spectrometer, especially relate to a kind of micro-probe of optical fiber of Tip-Enhanced Raman Spectroscopy instrument.
Background technology
Raman spectrum can cover frequency separation and water and the CO of complete molecular vibration because of it
2raman scattering intensity very weak and become a kind of important vibrational spectrum technology in chemistry, biology and investigation of materials.Surface enhanced raman spectroscopy (Surface-Enhanced Raman Scattering, SERS) discovery of phenomenon, promoted the detection sensitivity of Raman spectrum, make it in the various solid-liquids of research, solid/aerosphere face and living things system, show unique advantage, especially the discovery of unimolecule SERS, has promoted developing rapidly of SERS especially.But, SERS strengthen need the surface of nanoscale, restriction that spatial resolution is subject to diffraction limit and SERS mechanism still the key issue such as unclear all restrict to a certain extent SERS and develop into important tool (1.Tian, the ZQ in Surface Science and analysis science; Ren, B; Li, JF; Yang, ZL.Chemical Communications, (34): 3514-3534,2007).
And about 2000, several different research groups have proposed Tip-Enhanced Raman Spectroscopy technology (Tip-Enhanced Raman Spectroscopy) independently in the world, referred to as TERS.TERS technology can produce the metal probe (as Ag, Au) of surface plasma body resonant vibration as the needle point of SPM (scanning probe microscopy), by SPM, needle point will be controlled to the distance (as 1nm) very near with sample.When the laser of suitable wavelength is radiated to the end of needle point in appropriate mode (incident angle and polarization direction), just may between needle point and sample, inspire the surface plasma body resonant vibration of localization, electromagnetic field in this region is strengthened greatly, and then strengthen the Raman signal of molecule in this interval.Because enhancing source is the electromagnetic field of tip end height localization, so TERS has high spatial resolution and high sensitivity.TERS technology, after report in 2000, causes and pays close attention to widely (2.Pettinger, B.Ren, G.Picardi, R.Schuster, and G.Ertl, Phys.Rev.Lett.92,096101_2004_) both at home and abroad.
TERS is the coupling technique of SPM and Raman spectrum, how two kinds of instruments is coupled well and makes it not only possess the high spatial resolution of SPM instrument but also have the key that very high Raman detection sensitivity becomes this technology.At present, the TERS instrument of commercialization and Custom Prosthesis, all by large-scale Raman spectrometer, commercial microscope and the mechanically coupling of scanning force microscope three instrument, this causes that instrument overall volume is huge, light path is complicated, the phase mutual interference between three cover systems, cause SPM system works unstable, also cause the high (3.http: //ntmdt.com/device/ntegra-spectra of instrument price; 4.http: //www.renishaw.com/en/afm-raman-system-6638; 5.http: //www.nanonics.co.il/combined-microraman-and-nsom-spm-syst em.html; 6.http: //www.horiba.com/scientific/products/raman-spectroscopy/ra man-systems/hybrid-raman/raman-afm/); When SPM Instrument crosslinking with other type, be subject to the restriction in SPM probe space, lack versatility.
Summary of the invention
The object of the present invention is to provide that a kind of light path is simple, small volume, conveniently replaced optical maser wavelength and polarization direction, there is better stability, can with the coupling of any scan-probe microsurgical instrument, can conveniently switch excitation mode, as reflective excitation mode and transmission-type excitation mode, can improve the micro-probe of optical fiber of the resistance to overturning of TERS instrument and the Tip-Enhanced Raman Spectroscopy instrument of ease-to-operate.
The present invention is provided with box body and circuit part, and described circuit part is located in box body;
Described circuit part is provided with white light imaging optical path, laser optical path and signal collection light path; Described white light imaging optical path, laser optical path and signal collection light path all adopt fiber optic conduction;
Described white light imaging optical path is provided with optical fiber, the 1st beam splitter, the 2nd beam splitter, microlens, lens, catoptron, camera and pull bar, and white light enters after probe by optical fiber, after the 1st beam splitter reflection, enters microlens, focuses on sample; Then after the signal of sample is collected by microlens, by the 2nd beam splitter reflection, through after lens, be reflected mirror reflection, enter camera imaging;
Described laser optical path is provided with the edge filter sheet that laser instrument, single-mode polarization maintaining fiber, fiber coupler, laser rays band pass filter and 45 degree are placed; The laser that laser instrument produces enters probe by single-mode polarization maintaining fiber and fiber coupler, through laser rays band pass filter, then after the edge filter sheet of placing through 45 degree reflection, enters microlens, and focuses on sample or needle point;
Described signal collection light path is provided with 0 degree and places edge filter sheet, fiber coupler, multimode optical fiber and spectroscopic detector; After Raman or fluorescence signal are collected by microlens, the edge filter sheet of directly placing through 45 degree and 0 degree are placed after edge filter sheet, and filtering exciting light, enters fiber coupler, and is transferred in spectroscopic detector through multimode optical fiber.
Described box portion left side can be provided with for the fixing tapped through hole of microlens; Box portion right side can be provided with 2 through holes for difference fixed imaging CCD and fiber coupler; Box body front surface can be provided with 2 holes that are respectively used to installing optical fibres and tie-bar, and box body rear surface can be provided with the through hole for fixed fiber coupling mechanism, all light path coaxials.
In box body, can be provided with for demarcating and the spacing mark of fixing optical element.
Focused on after sample, can utilize pull bar or electronic transfer table that the 1st beam splitter and the 2nd beam splitter are pulled open, avoided block signal to collect light path.
The edge filter sheet that described 45 degree are placed can be replaced by half-reflection and half-transmission beam splitter.In described light path, the polarizer can be set, for changing polarization direction.
Described signal collection light path can adopt multimode optical fiber.
Principle of the present invention is:
By laser optical path, signal collection light path and white light imaging optical path are all integrated in the miniature probe of small volume, incident, collection, illuminator all adopt Optical Fiber Transmission.This probe is possessed all Core Features of the burnt micro-Raman spectroscopy of large-scale copolymerization: laser excitation, Raman signal are collected, micro-imaging, and copolymerization is burnt.Wherein input path adopts single-mode polarization maintaining fiber transmission, guarantee that laser polarization property in transmitting procedure is constant, collect light path and adopt multimode optical fiber transmission (focusing performance regulates and controls by collecting the core diameter of optical fiber altogether), can carry out wide spectrum band Raman or fluorescence signal and detect.Excitation Filter with High choice for use angle is 0 degree or 45 degree edge optical filters, and making all optical axises is all 0 degree and 90 degree, does not need to change other optical element while making to change excitation wavelength.
Compared with prior art, the present invention has following outstanding advantage and technique effect:
1) in the present invention, excite, collection, imaging optical path be all integrated in fibre-optical probe, small volume, improves instrument resistance to overturning greatly.Because instrumental optics of the present invention part is all integrated in optic probe, therefore can switch easily, anti-two kinds of excitation modes.
2) in the present invention, having adopted Excitation Filter with High is edge optical filter (edge filter), compare with the instrument of employing notch filtering light sheet (notch filter), the angle that edge optical filter is used can be 0 degree or 45 degree, making angle between optical axis is all 0 degree or 90 degree, has simplified greatly light path.And adopting notch filtering light sheet, its use is limited in an extremely special angle: 9 degree～12 degree left and right, this will cause light path design complicated.In addition, the operating angle of notch filtering light sheet is extremely responsive to air humidity, and this will cause instrument unstable; And edge optical filter can be avoided these problems.
3) input path of the present invention adopts single-mode polarization maintaining fiber transmission, guarantees that laser polarization property in transmitting procedure is constant.
4) all optical axises all adopt 0 degree or 90 degree designs, make optical path adjusting simple; In light path, can add arbitrarily the optical element of other function; When changing excitation wavelength, do not need any optical element of change except edge optical filter.
5), in the present invention, the optical element usage quantity in probe, far fewer than large-scale Raman spectrometer, has reduced light loss, has greatly improved detection efficiency.
6) pinpoint enhanced Raman of the present invention probe can with the coupling of any commercial SPM system.Opticator volume ratio commercialization instrument has dwindled more than 90%, and Costco Wholesale is low, for really making this high spatial resolution of TERS, highly sensitive detection technique be widely used in scientific research, industry and lay the foundation.
7) the present invention can be used as normal miniature Raman spectrometer for conventional Raman spectrum and Surface enhanced raman spectroscopy detection.
Accompanying drawing explanation
Fig. 1 is that the structure of the embodiment of the present invention forms schematic diagram.
Embodiment
The invention will be further described in connection with accompanying drawing for following examples.
Embodiment 1
Referring to Fig. 1, the embodiment of the present invention is provided with box body and circuit part, and described circuit part is located in box body;
Described box portion left side is provided with for the fixing tapped through hole of microlens 4; Box portion right side is provided with 2 through holes for difference fixed imaging CCD7 and fiber coupler 16; Box body front surface is provided with 2 holes that are respectively used to installing optical fibres 1 and tie-bar 8, and box body rear surface is provided with the through hole for fixed fiber coupling mechanism 11, all light path coaxials.
Described circuit part is provided with white light imaging optical path, laser optical path and signal collection light path; Described white light imaging optical path, laser optical path and signal collection light path all adopt fiber optic conduction.
Described white light imaging optical path is provided with optical fiber 1, the 1st beam splitter the 2, the 2nd beam splitter 3, microlens 4, lens 5, catoptron 6, camera 7 and pull bar 8, white light enters after probe by optical fiber 1, after the 1st beam splitter 2 reflections, enter microlens 4, focus on sample; Then after the signal of sample is collected by microlens 4, by the 2nd beam splitter 3 reflections, through after lens 5, be reflected mirror 6 reflections, enter camera 7 imagings.
Described laser optical path is provided with the edge filter sheet 14 that laser instrument 9, single-mode polarization maintaining fiber 10, fiber coupler 11, laser rays band pass filter 12 and 45 degree are placed; The laser that laser instrument 9 produces enters probe by single-mode polarization maintaining fiber 10 and fiber coupler 11, through laser rays band pass filter 12, then after edge filter sheet 14 reflections of placing through 45 degree, enters microlens 4, and focuses on sample or needle point.
Described signal collection light path is provided with 0 degree and places edge filter sheet 15, fiber coupler 16, multimode optical fiber 17 and spectroscopic detector 18; After Raman or fluorescence signal are collected by microlens 4, the edge filter sheet 14 of directly placing through 45 degree and 0 degree are placed after edge filter sheet 15, and filtering exciting light, enters fiber coupler 16, and is transferred in spectroscopic detector 18 through multimode optical fiber 17.
In box body, can be provided with for demarcating and the spacing mark of fixing optical element.Focused on after sample, can utilize pull bar 8 or electronic transfer table that the 1st beam splitter 2 and the 2nd beam splitter 3 are pulled open, avoided block signal to collect light path.
The edge filter sheet 14 that described 45 degree are placed can be replaced by half-reflection and half-transmission beam splitter.In described light path, the polarizer 13 can be set, for changing polarization direction.
Described signal collection light path can adopt multimode optical fiber.
Described box body can adopt cube.
In TERS experiment, in order effectively to excite the surface plasma of the local of metal needle point, must make the polarization direction of laser be parallel to needle point axial direction.General oblique incidence and two kinds of modes of bottom incident of adopting.Bottom incident mode is applicable to study transparent sample, as living things systems such as cells.Because instrumental optics part of the present invention is all integrated, therefore can switch easily two kinds of patterns, only need to adopt two kinds of different types of focusing, inner light path does not need to do any change.
Claims (4)
1. the micro-probe of the optical fiber of Tip-Enhanced Raman Spectroscopy instrument, is characterized in that being provided with box body and circuit part, and described circuit part is located in box body;
Described circuit part is provided with white light imaging optical path, laser optical path and signal collection light path; Described white light imaging optical path, laser optical path and signal collection light path all adopt fiber optic conduction;
Described white light imaging optical path is provided with optical fiber, the 1st beam splitter, the 2nd beam splitter, microlens, lens, catoptron, camera and pull bar, and white light enters after probe by optical fiber, after the 1st beam splitter reflection, enters microlens, focuses on sample; Then after the signal of sample is collected by microlens, by the 2nd beam splitter reflection, through after lens, be reflected mirror reflection, enter camera imaging;
Described laser optical path is provided with the edge filter sheet that laser instrument, single-mode polarization maintaining fiber, fiber coupler, laser rays band pass filter and 45 degree are placed; The laser that laser instrument produces enters probe by single-mode polarization maintaining fiber and fiber coupler, through laser rays band pass filter, then after the edge filter sheet of placing through 45 degree reflection, enters microlens, and focuses on sample or needle point;
Described signal collection light path is provided with 0 degree and places edge filter sheet, fiber coupler, multimode optical fiber and spectroscopic detector; After Raman or fluorescence signal are collected by microlens, the edge filter sheet of directly placing through 45 degree and 0 degree are placed after edge filter sheet, and filtering exciting light, enters fiber coupler, and is transferred in spectroscopic detector through multimode optical fiber;
Described box portion left side is provided with for the fixing tapped through hole of microlens; Box portion right side is provided with 2 through holes for difference fixed imaging CCD and fiber coupler; Box body front surface is provided with 2 holes that are respectively used to installing optical fibres and pull bar, and box body rear surface is provided with the through hole for fixed fiber coupling mechanism, all light path coaxials;
In box body, be provided with for demarcating and the spacing mark of fixing optical element.
2. the micro-probe of the optical fiber of Tip-Enhanced Raman Spectroscopy instrument as claimed in claim 1, is characterized in that the edge filter sheet of described 45 degree placements is replaced by half-reflection and half-transmission beam splitter.
3. the micro-probe of the optical fiber of Tip-Enhanced Raman Spectroscopy instrument as claimed in claim 1, is characterized in that, on described laser optical path, the polarizer is set, for changing polarization direction.
4. the micro-probe of the optical fiber of Tip-Enhanced Raman Spectroscopy instrument as claimed in claim 1, is characterized in that described signal collection light path adopts multimode optical fiber.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102928397B (en) * | 2012-11-07 | 2015-11-04 | 厦门大学 | Holographic Tip-Enhanced Raman Spectroscopy instrument optical system |
| CN104267488B (en) * | 2014-10-11 | 2017-04-12 | 中国科学院重庆绿色智能技术研究院 | Optical microscope beam splitter device |
| CN104949958B (en) * | 2015-06-26 | 2024-02-20 | 北京杏林睿光科技有限公司 | Novel Raman probe based on optical fiber beam splitter |
| CN107290308B (en) * | 2016-04-01 | 2021-01-05 | 高利通科技（深圳）有限公司 | Combined type spectrum probe and spectrum analysis system |
| CN105973868A (en) * | 2016-05-09 | 2016-09-28 | 西北工业大学 | Optical fiber vector optical probe type tip-enhanced Raman spectroscopy and spectrum collection method |
| CN106770182B (en) * | 2017-03-24 | 2023-11-21 | 钢研纳克检测技术股份有限公司 | Portable Raman spectrometer with CCD turning light path |
| CN108717057A (en) * | 2018-05-31 | 2018-10-30 | 中央民族大学 | A kind of portable surface enhancing Raman spectrometer and its measurement method |
| CN110967330B (en) * | 2018-09-30 | 2022-12-02 | 中国计量科学研究院 | Micro-area confocal Raman spectrum detection system |
| US11156636B2 (en) | 2018-09-30 | 2021-10-26 | National Institute Of Metrology, China | Scanning probe having micro-tip, method and apparatus for manufacturing the same |
| CN110260974A (en) * | 2019-07-15 | 2019-09-20 | 天津大学 | Microscopic Raman detecting devices |
| CN113008862B (en) * | 2021-02-03 | 2022-06-24 | 中国海洋大学 | Underwater Raman probe and underwater detection system |
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| US7916291B2 (en) * | 2006-06-13 | 2011-03-29 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Apparatus and method for spectroscopy |
| US7929131B2 (en) * | 2009-04-23 | 2011-04-19 | Enwave Optronics, Inc. | Highly compact design for raman spectrometry |
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| CN101082585A (en) * | 2007-07-19 | 2007-12-05 | 清华大学 | Reflexion type near-field Raman spectrometer instrument head |
| CN101923054A (en) * | 2009-06-12 | 2010-12-22 | 中国科学院上海硅酸盐研究所 | Non-aperture tip enhanced Raman scattering probe and manufacturing method thereof |
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